Dipolar addition to cyclic vinyl sulfones leading to dual conformation tricycles

Abstract

Dipolar addition of cyclic azomethine imines with cyclic vinyl sulfones gave rise to functionalized tricycles that exhibited fluxional behavior in solution at room temperature. The scope of the synthetic methodology was explored, and the origin of the fluxional behavior was probed by NMR methods together with DFT calculations. This behavior was ultimately attributed to stereochemical inversion at one of two nitrogen centers embedded in the tricyclic framework. Two tetracycles were also synthesized, and the degree of signal-broadening in the NMR spectra was found to depend on the presence of substitution next to the inverting nitrogen center.